EP2114561A1 - Catalyseurs contenant des composés de tungstène et procédé de déshydratation de glycérine - Google Patents

Catalyseurs contenant des composés de tungstène et procédé de déshydratation de glycérine

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Publication number
EP2114561A1
EP2114561A1 EP07857691A EP07857691A EP2114561A1 EP 2114561 A1 EP2114561 A1 EP 2114561A1 EP 07857691 A EP07857691 A EP 07857691A EP 07857691 A EP07857691 A EP 07857691A EP 2114561 A1 EP2114561 A1 EP 2114561A1
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EP
European Patent Office
Prior art keywords
catalyst
compounds
glycerol
catalysts
dehydration
Prior art date
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Granted
Application number
EP07857691A
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German (de)
English (en)
Other versions
EP2114561B1 (fr
Inventor
Hubert REDLINGSHÖFER
Christoph Weckbecker
Klaus Huthmacher
Andreas DÖRFLEIN
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication of EP2114561A1 publication Critical patent/EP2114561A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for the production of acrolein from glycerol using an acidic catalyst comprising tungsten-containing compounds and at least one further promoter.
  • Acrolein is an important intermediate and of great economic importance for the preparation of acrylic acid, D, L-methionine and the methionine hydroxy analog 2-hydroxy-4-methylthiobutyric acid (MHA).
  • Methionine is an essential amino acid which i.a. is used as a supplement in animal feed.
  • Nutrit foundedsverêtnde feed additives are now an indispensable part of animal nutrition. They serve the better utilization of the food supply, stimulate the growth and promote the protein formation.
  • One of the most important of these additives is the essential amino acid methionine, which occupies a prominent position as a feed additive, especially in poultry rearing.
  • methionine substitutes such as the methionine-hydroxy analog (abbreviated MHA) have not insignificant importance, since they have similar growth-stimulating properties as the known amino acid.
  • Acrylic acid is an important starting material for the preparation of polymers which are used, for example, as superabsorbents because of their water absorption capacity.
  • EP 0598229 US 5387720 also describes the acid-catalyzed conversion of glycerol to acrolein in the gas phase and in the liquid phase. In it alone determines the acidity (Hammet's acidity) the suitability as a catalyst.
  • DE 42 38 492 relates to the synthesis of 1,2 and 1,3 propanediol by dehydration of glycerol in high yields.
  • WO 2006/087083 discloses a process for preparing acrolein from glycerol over acidic catalysts, in which oxygen is added to the reaction mixture. A similar process is described in WO 2006/087084.
  • the catalysts used there have a Hammett acidity Ho in the range of -9 to -18.
  • the object of the invention is to provide a catalyst for the dehydration of glycerol, which shows a lower tendency to coke and is easily regenerable.
  • the invention relates to tungsten compounds containing solid catalysts having a Hammett acidity H 0 of ⁇ +2 containing one or more promoters selected from compounds of the group of elements containing, in particular consisting of gold, silver, copper,, platinum, rhodium, Palladium, ruthenium, samarium, cerium, yttrium, scandium, lanthanum,,, zinc, magnesium, iron, cobalt or nickel or mixtures thereof.
  • Acid zeolites or montmorillonite are particularly suitable as promoters, which then optionally in each case in an amount of 0.1 to 30 wt .-%, in particular 5 to 25 wt .-%, based on the catalyst, in addition to the abovementioned promoters or exist alone.
  • individual ones of the stated elements can also be present in metallic form on the catalyst.
  • catalysts which have a Hammett acidity H 0 of ⁇ + 2 to -20.
  • a process is also provided for the preparation of acrolein from glycerol, in which these catalysts are used.
  • glycerol is a reactive molecule that tends to form higher boiling compounds especially at high temperatures by having two or more
  • the catalyst of the invention contains one or more promoters which accelerate the regeneration of the catalyst.
  • service life and space-time yield increase significantly, since above all the deactivation by coking in these catalysts is at least largely eliminated and the activity is significantly increased.
  • the conversion of glycerin and the yield to acrolein can be maintained at a high level as a function of time. This is particularly important for a technical implementation of the synthesis of great importance, since a change of the catalyst and associated plant downtime cause high costs.
  • Catalyst selected from the group consisting of silicon, phosphorus, niobium, zinc, tin, magnesium, aluminum or molybdenum modify the surface of the catalyst or reduce the concentration of active sites, so that the selectivity is further improved. Specifically, the formation of solid adsorbed high boilers or coke precursors formed from two or more adjacent adsorbed glycerol molecules or intermediates is thereby reduced.
  • These compounds thus also serve to reduce the concentration of active sites on the catalyst surface and thus increase the distance between adjacent active sites (site isolation). This, in turn, reduces the likelihood that two glycerin molecules or formed reactive intermediates or coke precursors will surface react to higher hydrocarbons.
  • solid-state catalysts are the types known from US Pat. No. 5,387,720 (EP 0 598 229 A1), if they additionally contain a tungsten compound and one or more of the promoters mentioned. These are solid, in the reaction medium substantially insoluble mono- or poly-phase substances having an H o value less than +2, preferably less - 3.
  • the H o value corresponds to the acid function of Hammett and can be by the so-called amine titration using indications or by adsorption of a gaseous base - see Studies in surface science and Catalysis, Vol. 51, 1989: "New solid acids and bases, their catalytic properties" by K.
  • oxides and mixed oxides such as ⁇ -Al 2 O 3 and ZnO-Al 2 O 3 -, SiO 2 -Al 2 O 3 -, ZrO 2 -SiO 2 , ZrO 2 -HfO 2 - mixed oxides or heteropolyacids.
  • Suitable compounds for providing the active tungsten centers may be, for example, ammonium tungstate, ammonium metatungstate, tungstic acid, tungsten silicic acid, tungstophosphoric acid, tungsten oxides or heteropolyacids with tungsten as an ingredient. These compounds or their mixtures are then either used directly as a catalyst or used as catalyst precursors. With the addition of further elements is preferably a previous mixture as a powder, in one
  • the catalytically active compounds are bound on a support.
  • carrier materials for example, alumina, titania, silica, zirconia, activated carbon or mixtures thereof may be used.
  • the carriers are used primarily to increase the specific surface area or to fix the active sites.
  • the catalysts according to the invention are prepared by methods known to the person skilled in the art. If the active components are applied to a carrier, this is preferably done by impregnating the carrier, for example by means of the incipient wetness method by spraying. The active components can also be recovered by precipitation or extraction from solution. Then, a shaping of the catalyst can optionally be carried out with the addition of carriers, adhesion promoters or pore formers by pressing, extrusion, coating or agglomeration.
  • the catalyst usually has a particle diameter between 0.04 mm and 20 mm, preferably between 0.1 and 10 mm, in particular between 0.5 and 7 mm.
  • the active compounds may also be applied in the form of a shell. If no support is used, catalyst preparation by extrusion, tablet pressing or buildup agglomeration is preferred.
  • catalysts having an H o value between -3 and -8.2 are particularly preferred; , Suitable catalyst systems which contain tungsten compounds and promoters are, for example, Pd / H 2 WO 4 , Pt / H 2 WO 4 , Pd / WO x / ZrO 2 , Cu / WO x / ZrO 2 .
  • the invention also relates to a process for the preparation of acrolein by dehydration of glycerol in the presence of tungsten-containing solid catalysts having a Hammett acidity Ho of ⁇ +2 to preferably -20, containing one or more promoters selected from compounds of the group of Elements containing, preferably consisting of gold, silver, copper, platinum, palladium, rhodium, ruthenium, samarium, cerium, yttrium, scandium, lanthanum, zinc, magnesium, iron, cobalt or nickel or mixtures thereof and optionally additionally containing compounds of the elements Lithium, sodium, potassium or cesium and / or montmorillonite or acidic zeolites, these compounds being optionally present in an amount of 0.1 to 30 wt .-%, in particular 5 to 25 wt .-%, based on the catalyst.
  • the dehydration is preferably carried out in the absence of oxygen. In one embodiment, in the presence of hydrogen in an amount of 0.1 to 10 vol.%, In particular from 0.5 to 5%, based on the total amount of the reaction mixture.
  • the dehydration is carried out in the presence of the catalysts described above.
  • the concentration of glycerol in the reaction mixture is preferably by the admixture of the selected Reaction conditions lowered inert suitable gaseous compounds.
  • Solvents and diluents known to those skilled in the art are used, such as, for example, water, nitrogen, air, carbon dioxide, methane and / or hydrogen, alcohols, for example methanol and ethanol, acetone, toluene or methyl isobutyl ketone. Preference is given to Verdunnungsmedien that can be easily isolated from acrolein after condensation by phase separation.
  • the glycerol concentration is between 1 and 100% by weight, preferably between 1 and 70% by weight and in particular between 5 and 40% by weight.
  • Glycerine solutions with a content of 5 to 40 wt .-% are usable.
  • so-called crude glycerols can be used directly for the synthesis of acrolein without prior concentration or purification.
  • the reaction is carried out at a temperature between 150 and 450 ° C., preferably between 180 and 350 ° C., more preferably between 220 and 320 ° C.
  • the pressure is between 0.1 and 200 bar, preferably between 0.5 and 50 bar, more preferably between 0.9 and 10 bar.
  • the process can be in the Flussigphase or in the
  • the reaction in the gas phase is particularly preferred because the glycerine conversion is practically complete (> 95%). and the gaseous reaction mixture leaving the catalyst can be directly condensed or absorbed to give an aqueous acrolein solution containing additionally formed by-products; This condensate can often be further processed directly.
  • the partial condensation and / or absorption of the reaction mixture can take place in several stages. If desired, from the reaction mixture acrolein, optionally together with a portion of the water, by fractional condensation, absorption,
  • Part of the water is recycled, where it is vaporized and condensed using heat integration.
  • An inert gas or a diluent can also be recycled.
  • acrolein is separated from the reaction mixture alone or together with part of the water and small amounts of by-products in a known manner, usually by distillation, by desorption or by N 2 ⁇ stripping.
  • the acrolein can pass through
  • the dehydration in the gas phase is preferably carried out in the temperature range between 240 and 320 0 C, those in the
  • Liquid phase preferably between 200 and 300 0 C.
  • the apparatus is subjected to at least such a pressure that is required to maintain the liquid phase.
  • the dehydration takes place in a fixed bed reactor, a fluidized bed reactor, in a reactor with a circulating fluidized bed, a moving bed reactor or a reactor with regenerator-riser (downer) concept. It can be carried out continuously or discontinuously.
  • the combination of the reaction with a Eduktaufleung or product workup by means of a reactive distillation is possible or useful, since the boiling point differences between glycerol and acrolein are very large.
  • the catalyst is placed either in the sump and / or in the column section.
  • the introduced catalyst can be present for example in the form of a bed, suspension or a coating.
  • Another advantage of the reactive distillation is that heavy-boiling impurities are discharged from crude glycerol at the bottom of the column with further high-boiling components which can be formed as by-products. Acrolein and low boilers are then taken off overhead.
  • Formed acrolein can also be separated from the reaction mixture in a known manner, alone or together with part of the solvent or dilution medium, by stripping, distillation or extraction. Unreacted glycerin can then be recycled to the reaction stage.
  • a process is also provided, in particular for the preparation of methylmercaptopropionaldehyde (MMP) from glycerol without isolation of intermediates, wherein the multi-stage synthesis of MMP according to the prior art can now be carried out in one stage using the catalyst according to the invention.
  • MMP methylmercaptopropionaldehyde
  • R H, Ci to C 3 alkyl, by the reaction with glycerol or with a compound from which glycerol is formed with a compound of the general formula
  • R H, Ci to C 3 alkyl in the presence of the inventive catalyst.
  • Preferred product is MMP made using methylmercaptan.
  • a glycerol-methylmercaptan mixture if appropriate in the presence of a solvent, is reacted either in the liquid phase or in the gas phase over a solid catalyst according to the invention.
  • the pressure is adjusted such that the liquid state of the reaction mixture is maintained.
  • the pressure is usually between 1 and 300 bar, preferably between 5 and 200 bar, more preferably between 20 and 150 bar
  • the catalyst according to the invention is also distinguished by a good regenerability and a slow deactivation / coking.
  • the regeneration can take place on the one hand under oxidation conditions on the other hand under hydrogenation conditions.
  • the coke which has formed during the reaction on the surface of the catalyst by deposition of hydrocarbons, partially or completely removed.
  • the suitable promoters which form part of the catalyst are generally components which accelerate the conversion of hydrocarbons to carbon oxides, such as
  • the acidic catalyst preferably contains promoters having a strongly hydrogenating action, for example compounds of the elements cobalt, nickel, palladium, platinum, ruthenium or rhodium, individually or in a mixture, optionally also in elemental form. Furthermore, a combination of several effects by addition of one or more promoters is possible.
  • the regeneration is either temporally or locally separated from the reaction of glycerol.
  • the feed of glycerol is stopped in this reactor and then carried out the regeneration, before again the starting material mixture is fed. This process is repeated periodically as often as desired.
  • this regeneration method in particular the timing of 2 or more fixed bed reactors to a be able to show continuous product flow.
  • one of the reactors is regenerated, while at least one of the reactors is used for the production of acrolein.
  • the time intervals for reaction and regeneration can be chosen arbitrarily.
  • the uninterrupted production of acrolein within a time interval of 2 to 3000 h, in particular 4 to 400 h before the catalyst is regenerated in a time interval of 0.5 to 100 h, in particular 1 to 10 h.
  • Suitable reactor concepts are the moving bed reactor or the
  • the moving bed is characterized by a lower throughput of the catalyst and less catalyst abrasion and is preferred here.
  • a higher temperature is used for the regeneration of the catalyst than in the reaction.
  • the pressure during the regeneration is preferably between 0 and 50 bar, in particular between 0 and 3 bar.
  • At least one additive is used to regenerate the catalyst.
  • This is preferably gaseous. When regenerated under oxidizing conditions, it is a gaseous oxidizer. Preference is given to air or oxygen or carbon dioxide used.
  • Regenerated by hydrogenation is a gaseous reducing agent. Preferably, hydrogen is then used.
  • the reducing gas is preferably used diluted, including, for example, nitrogen or water vapor can be used.
  • the concentration of the additive is preferably increased gradually.
  • the catalyst can be diluted by solid inert material or else arranged in different zones.
  • the desired catalytic properties and / or the acid function of the catalyst does not disappear during the regeneration of the catalysts according to the invention, as is observed, for example, in the catalysts prepared using classical acids such as phosphoric acid or hydrochloric acid and leads to catalyst deactivation.
  • a catalyst was used according to patent DE 4238493: 100 g silica carrier with a diameter of about 4 mm were mixed with 25 g of a 20 wt .-% phosphoric acid for 1 h. The excess water was then removed at about 70 ° C. on a rotary evaporator. 18 ml of this catalyst was placed in a 15 mm diameter fixed bed reactor. The reactor was then heated to a temperature of 250 ° C. By means of a pump 12.5 g / h of a 20 wt .-% aqueous glycerol solution were passed through a heated to 260 0 C evaporator in the reactor. By gas chromatography, the current at the reactor outlet was analyzed.
  • Example 1 Comparative Example 1 was repeated except that molybdic acid compressed into tablets was used as the catalyst. At a reactor temperature of 250 0 C within the first 5 h, a yield of 9% could be achieved. On a regeneration was waived.
  • Example 1
  • Comparative Example 1 was repeated except that tungstenic acid pressed into tablets was used as the catalyst.
  • a reactor temperature of 260 0 C a full degree of conversion and a yield of 79% could be achieved within the first 5 h.
  • the degree of conversion and accordingly the yield decreased significantly.
  • a drop in the yield of about 5% per 10 h was observed.
  • the activity of the catalyst could be significantly improved.
  • the glycerine substitution was then complete again at the beginning.
  • the degree of conversion and the yield decreased as described before the regeneration. This cycle of glycerine dehydration and catalyst regeneration was repeated three times over 300 h. After removal of the unregenerated catalyst this was colored black.
  • the carbon content of the catalyst was 22 wt .-%, which indicates a significant coking.
  • Tablets pressed tungstic acid was used as a catalyst.
  • This catalyst was additionally impregnated with 1% by weight of Pd.
  • Pd acetate was used by means of incipient wetness.
  • a reactor temperature of 260 0 C a full degree of conversion and a yield of 77% could be achieved within the first 5 h.
  • the degree of conversion and accordingly the yield decreased significantly.
  • the activity of the catalyst could be significantly improved.
  • the glycerine substitution was then complete again at the beginning. Compared to Example 1, the drop in the degree of conversion in the dehydration reaction after regeneration was significantly lower and the high level of conversion could be maintained longer.
  • Comparative Example 1 was repeated except that a powder mixture of 15% by weight pressed into tablets was used.
  • the glycerol replenishment was complete again after regeneration at the beginning. After passing through 6 cycles of dehydration and regeneration, the regeneration temperature was raised to 390 ° C. This resulted in the subsequent dehydration to a significantly increased degree of conversion profile, the Glycerin rate after about 20 h was still more than 90%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication d'acroléine à partir de glycérine, au moyen d'un catalyseur solide acide contenant des composés de tungstène et d'autres promoteurs. L'invention concerne également un procédé notamment destiné à la fabrication de méthylmercaptopropionaldéhyde à partir de glycérine, en présence du catalyseur.
EP07857691.5A 2007-01-29 2007-12-17 PROCÉDÉ DE DÉSHYDRATATION DE GLYCÉRINE en présence de CATALYSEURS CONTENANT DES COMPOSÉS DE TUNGSTÈNE Not-in-force EP2114561B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007004351A DE102007004351A1 (de) 2007-01-29 2007-01-29 Neue Katalysatoren und Verfahren zur Dehydratisierung von Glycerin
PCT/EP2007/064060 WO2008092533A1 (fr) 2007-01-29 2007-12-17 Catalyseurs contenant des composés de tungstène et procédé de déshydratation de glycérine

Publications (2)

Publication Number Publication Date
EP2114561A1 true EP2114561A1 (fr) 2009-11-11
EP2114561B1 EP2114561B1 (fr) 2016-11-02

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CN101652172A (zh) 2010-02-17
WO2008092533A1 (fr) 2008-08-07
US20100113833A1 (en) 2010-05-06
US7790934B2 (en) 2010-09-07
JP5227339B2 (ja) 2013-07-03
US20080183019A1 (en) 2008-07-31
BRPI0721034A2 (pt) 2014-07-29
MX2009007815A (es) 2009-07-31
CN101652172B (zh) 2014-03-05
BRPI0721034B1 (pt) 2017-04-04
EP2114561B1 (fr) 2016-11-02
JP2010516461A (ja) 2010-05-20
MY146792A (en) 2012-09-28
ES2611938T3 (es) 2017-05-11
RU2009132406A (ru) 2011-05-10
DE102007004351A1 (de) 2008-07-31

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